Carbonylation process

Abstract

A carbonylation process which comprises contacting a β-fluoroalkanol, carbon monoxide, a base, and the Group IIB element mercury present in an oxidation state greater than zero. The resulting β-fluoroaliphatic carbonates can be employed in combination with alkanols and/or phenols to prepare aliphatic and aromatic mono- and polycarbonates. The resulting carbonates are useful in a wide variety of applications, especially polycarbonates which can be molded or formed into films, sheets, fibers, laminates, or reinforced plastics by conventional techniques.

We claim: 
     
       1. A carbonylation process which comprises contacting a β-fluoroalkanol, carbon monoxide, a base, and the Group IIB element mercury present in an oxidation state greater than zero, and subsequently recovering at least a portion of a resulting β-fluoroaliphatic carbonate. 
     
     
       2. The claim 1 process, further comprising a solvent. 
     
     
       3. The claim 2 process, further comprising an aprotic solvent. 
     
     
       4. The claim 1, 2 or 3 process, wherein said element is present in an ionic form. 
     
     
       5. The claim 1, 2 or 3 process, wherein said element oxidation state is at least +1. 
     
     
       6. The claim 2 or 3 process, wherein said base is a sterically hindered amine. 
     
     
       7. The claim 1, 2 or 3 process, wherein said element oxidation state is at least +2. 
     
     
       8. The claim 1, 2 or 3 process, wherein said element is associated with a halide. 
     
     
       9. The claim 1, 2 or 3 process, wherein said element is coordinated with a ligand. 
     
     
       10. The claim 1, 2 or 3 process, wherein said element is associated with an inorganic halide compound. 
     
     
       11. A carbonylation process which comprises contacting a β-fluoroalkanol, carbon monoxide, a base, the Group IIB element mercury, and an oxidant having an oxidation potential greater than that of the Group IIB element, and subsequently recovering at least a portion of a resulting β-fluoroaliphatic carbonate. 
     
     
       12. The claim 11 process, comprising a solvent. 
     
     
       13. The claim 12 process, further comprising an aprotic solvent. 
     
     
       14. The claim 11, 12 or 13 process, wherein said element is present in an ionic form. 
     
     
       15. The claim 11, 12 or 13 process, wherein said element oxidation state is at least zero. 
     
     
       16. The claim 12 or 13 process, wherein said base is a sterically hindered amine. 
     
     
       17. The claim 11, 12 or 13 process, wherein said element oxidation state is at least +2. 
     
     
       18. The claim 11, 12, or 13 process, wherein said element is associated with a halide. 
     
     
       19. The claim 11, 12 or 13 process, wherein said element is coordinated with a ligand. 
     
     
       20. The claim 11, 12 or 13 process, wherein said element is associated with an inorganic halide compound. 
     
     
       21. The claim 11, 12 or 13 process, further comprising a redox co-catalyst. 
     
     
       22. The claim 11, 12 or 13 process, further comprising substantially anhydrous reaction conditions. 
     
     
       23. The claim 11, 12 or 13 process, further comprising a phase transfer agent. 
     
     
       24. The claim 22 process, further comprising a drying agent. 
     
     
       25. The claim 24 process, wherein the drying agent is a molecular sieve. 
     
     
       26. The claim 23 process, wherein the phase transfer agent is an onium halide. 
     
     
       27. The claim 3 process, wherein the solvent is dimethylsulfoxide, the base is 1,2,2,6,6-pentamethylpiperidine, the β-fluoroalkanol is 2,2,2-trifluoroethanol, the Group IIB element mercury is in the form of mercury(II) diacetate. 
     
     
       28. The claim 3 process, wherein the solvent is dimethylsulfoxide, the base is aqueous caustic, the β-fluoroalkanol is 2,2,2-trifluoroethanol, the Group IIB element mercury is in the form of mercury(II) diacetate. 
     
     
       29. A carbonylation process which comprises contacting 2,2,2-trifluoroethanol, carbon monoxide, 1,2,2,6,6-pentamethylpiperidine, mercury(II) diacetate, and subsequently recovering bis(2,2,2-trifluoroethyl) carbonate. 
     
     
       30. The claim 3 process wherein the β-fluoroalkanol is of the formula ##STR6## where at least one fluorine atom is associated with at least a β-carbon atom of the β-fluoroalkanol. 
     
     
       31. The claim 30 process wherein the β-fluoroalkanol is a β-trifluoroalkanol containing 2-10 carbon atoms. 
     
     
       32. A carbonylation process which comprises contacting a β-fluoroalkanol selected from   CH.sub.2 FCH.sub.2 OH,       CHF.sub.2 CH.sub.2 OH,       CF.sub.3 CH.sub.2 OH,       (CF.sub.3).sub.2 CHOH,       CF.sub.3 CF.sub.2 CH.sub.2 OH, ##STR7##       CF.sub.3 CF.sub.2 CF.sub.2 CH.sub.2 OH,     carbon monoxide, a base, and the Group IIB element mercury present in an oxidation state greater than zero, and subsequently recovering at least a portion of a resulting β-fluoroaliphatic carbonate.   
     
     
       33. A carbonylation process which comprises contacting a β-fluoroalkanol, selected from   CH.sub.2 FCH.sub.2 OH,       CHF.sub.2 CH.sub.2 OH,       CF.sub.3 CH.sub.2 OH,       (CF.sub.3).sub.2 CHOH,       CF.sub.3 CF.sub.2 CH.sub.2 OH, ##STR8##       CF.sub.3 CF.sub.2 CF.sub.2 CH.sub.2 OH,     carbon monoxide, a base, the Group IIB element mercury, and an oxidant having an oxidation potential greater than that of the Group IIB element, and subsequently recovering at least a portion of a resulting β-fluoroaliphatic carbonate.